DE2201030A1 - Azo dyes, their manufacture and use - Google Patents

Description

■ IT- ^

CIBA-GEIGY AG, CH-4Ü02 Basol

Case 1-73 ^ 3/1 + 2 Germany

2Ζ O 53 ft,

Azo dyes, their manufacture and use.

The invention relates to azo dyes, the remainder the coupling component the remainder of a dihydroxypyridine included, on which in addition in o-position to the azo bridge a Sufcstituent is bound, the at least one heteroatom contains, but the substituent must not be a halogen atom. It relates in particular to azo dyes, which are of the Forrre.

HO OH

(1) . I> -N = N— <ζ Ν

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correspond, in which D is the radical of a diazo component and X is a substituent which has at least one heteroatom contains, and which is bound in particular by a heteroatom to the dihydroxypyridine radical, and for the The above restriction applies.

The substituent X can be: a hydroxyl or alkoxy group, an H _? N or amino groups such as a methyl or phenylamino group or a group derived from a cyclic amine such as piperidine, an aryloxy group such as a phenoxy or naphthoxy group, the mercapto group or an alkyl or Ar $ mercapto group such as the methyl or phenyl mercapto group, a sulfonyl group, such as, for example, the methyl or phenylsulfonyl group and, above all, a water-solubilizing group, in particular the sulfonic acid group. Further possible substituents X are aminoalkylamino or andnoarylamino groups, such as, for example, the aminoethylamino group or an aminosulfophenylamino group, since these are obtained by acylation of the free amino group by means of a fiber-reactive acylation; can be introduced into the coupling component by means of a reactive radical.

Also important are dyes that contain a 5-substituted 2,3-dihydroxypyridyl (4) radical more than once definition given above, such as dyes

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the formula -

HO OH

⁽²⁾ _D ..- V%

HO OH

where D and D * each represent the remainder of a diazo component and R is the remainder of a diamine. D and D 'are preferred same.

Also of importance are the amine salts of dyes of the type according to the invention, the acidic water-soluble

Lightening groups, in particular sulfonic acid groups, contain. The amines used for salt formation are above all higher molecular weight and, in particular, quaternized amines. Salt formation with such amines makes the dyes insoluble in water, but instead alcohol or acetone-soluble and are therefore suitable for the dyeing of the pulp, e.g. suitable for cellulose esters.

The formation of cationic dyes by quaternizing dyes should also be considered of the formula (I), which in the 5-position contains the radical of an N, N-dialkylated alkylenediamine, such as, for example, N, N-dimethylpropylenediamine contain.

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Finally, as substituents X can also Hydroxy, amino, thiol and the like. Groups which are contained in fibrous materials such as cellulose fibers or polyamides are used are.

Of particular interest are the heavy metal complexes of the azo compounds of the formula (I), where as Complexing metals e.g. iron, manganese, nickel, copper, cobalt and chromium come into consideration. The heavy metal complexes can contain one or two molecules of azo compounds of formula (I) contain bonded to a metal atom (1: 1 or 1: 2 complexes). In 1: 2 complexes, however, one can also of the two ligand molecules be an azo compound that does not have the remainder of a 2,3-dihydroxypyridine as a coupling component has, e.g. a compound of the azobenzene type, the corresponding complex-forming groups contains.

The diazo component D represents an aromatic radical .dar, which itself can contain an azo group or which is derived from a compound of the anthraquinone, nitroaryl, phthalocyanine, stilbene series or the like. In particular but D is a heterocyclic radical. The diazo component D can

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as usual by halogen atoms, hydroxy, amino, alkyl, Aryl, alkoxy, aryloxy, acylamino, carboxy, sulfonic acid, nitro groups, etc. may be substituted. It is about Heavy metal complexes of the compounds according to the invention, the diazo component D must be in the ortho position to the azo bridge have a complexing substituent such as a hydroxy, amino or carboxy group.

Among the compounds of the formulas (1) and (2), the Are not bound to a heavy metal atom, both those that do not have water-solubilizing agents are of interest Contain groups, as well as in particular those that are water-soluble, e.g. contain sulfonic acid or carboxylic acid groups. In particular, the compounds can be one or have more than one reactive group, such as a halogenated propionic acid group.

In heavy metal complexes of azo compounds of the formulas (1) and (2), one or more water-solubilizing groups should be present. It can also be bonded to one or more reactive groups for the Case that the heavy metal complex only has compounds of the formulas (1) or (2) as ligands, in particular are contained in the diazo components of the complexed azo compounds.

In 1: 2 complexes, in which from one molecule one Compound of the formulas (1) and (2) an azo compound which

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does not have a 2,3-dihydroxypyridine as a coupling component, is bound as a ligand, a reactive radical can in particular also be contained in the diazo or in the coupling component of the azo compounds in question.

The heterocyclic diazo components are preferred 5- or 6-membered heterocyclic radicals. These Residues can in particular two or more heteroatoms, especially nitrogen atoms, such as in the imidazole, thiadiazole or triazole radical, or they can contain a fused-on benzene radical, such as in the quinoline radical. The azo group can be bonded to the heterocycle itself or to the fused-on radical free of heteroatoms be. The diazo radicals can contain further substituents, such as halogen atoms, nitro, alkyl, alkoxy, Aryl, phenyl, acylamino, carboxy or arylazo groups and in particular sulfonic acid groups and reactive radicals all reactive atoms bound via amino groups or aliphatic carboxylic acid residues containing reactive atom groups, such as the α, ß-dibromopropionyl or a-bromoacrylic radical.

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Heavy metal coraplexes of azo compounds of the formula are of interest. ·

HO OH

D-IT = N

where D is a quinoline residue bonded in the 8-position, and especially heavy metal complexes of azo compounds of the formula

^ ~ \ HO OH / L— (VN = N- -f ^X N (4)

correspond, in which Z is a halogen atom, e.g. a chlorine atom, a sulfonic acid or acylamino group, such as the acetylamino group, or an arylazo group. as The arylazo group is particularly the phenyiazo group, which preferably contains a reactive radical, such as e.g. in the ksazo compound of the formula

HO OH

NHGOCHBrCH ₂ Br

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/ (3 ) to (5) / The slide residues, which one of the formula /

Form speaking structure, do not need to contain any of the usual complex-forming groups, such as hydroxyl, carboxy or alkoxy groups, since the metal atom, except for the HO group ortho to the azo group of the remainder of the coupling component, to the azo group and to the im heterocyclic diazo radical containing a lone pair of electrons having nitrogen atom is coordinated. In this way, a metal atom with a molecule of formula (4), for example, forms a five-membered and a six-membered ring, and a metal atom with two molecules of formula (h) forms two five-membered and two six-membered rings, structures that are particularly stable distinguish. The charge of the ion containing the metal atom depends on whether acidic groups, in particular sulfonic acid groups, or basic groups, such as, for example, quaternized amino groups, are present.

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Of the heavy metal complexes of the formulas (3) to (5) according to the invention, both those of interest are which do not contain any water-solubilizing groups, as well as especially those which are water-soluble, e.g. sulfonic acid or contain carboxylic acid groups and one or more than one reactive radical.

Reactive radicals react with the hydroxyl groups of cellulose or the amino groups of Polyamides capable of forming a covalent chemical bond into consideration. Such Grouping represents, in particular, a low molecular weight group that can be split off by an atom or group substituted alkanoyl or alkylsulfonyl radical, a low molecular weight, optionally substituted by a removable atom or a removable group Alkenoyl or alkenesulfonyl radical, one via a carbonyl or sulfonyl group, by a removable atom or a Removable group substituted carbo- or heterocyclic, 4-, 5- or 6-ring containing radical or a bonded directly via a carbon atom, substituted by a removable atom or a removable group Triazine or pyrimidine radical or contains one. The reactive radical is preferably one via an —NH group bonded aliphatic saturated or unsaturated acyl radical, preferably containing halogen atoms, in particular the α, ß-dibromopropionyl or α-bromoacrylic radical.

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The dyes according to the invention are prepared by using azo dyes, which are the remainder of the Coupling component contain the remainder of a dihydroxypyridine, on which a halogen atom in o-position to the azo bridge is bonded, reacts with substituting compounds which contain a radical containing at least one heteroatom - The reaction is preferably carried out in aqueous solution at a slightly or only moderately elevated temperature and in the event of a weakly acidic, neutral or weakly alkaline reaction, especially in the presence of suitable buffer substances,

Azo dyes, in particular, are used as starting compounds the formula

HO (6) BNN

Y
contemplated in which D is the residue of a diazo component and Y is

Means halogen atom. ^y

As compounds which contain a radical which has at least one heteroatom, and those for the preparation ■ of the dyes according to the invention are suitable, the following may be mentioned: aliphatic or aromatic amines, alcohols * phenols, naphthols, mercaptans, such as thiophenol, alkali sulfinates, Alkali sulfites or alkali sulfides, alkali cyanides, alkali rhodanides, alkali thiosulfates and the like, by which

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the corresponding remainders, e.g. those mentioned at the beginning, in 5-position introduced with elimination of the halogen atom will. Instead of relatively simple, low molecular weight compounds, dyes can also be used as reactants are used which have one or more than one corresponding group containing a heteroatom, e.g. via a free amino group. In this way, several chromogens can be linked together and through the Mixing the nuances certain tones can be obtained.

Substituting components which contain at least one heteroatom are specifically mentioned: Methylamine, 'ethylamine, ri-propylamine, isopropylamine, n-butylamine, Cyclohexylamine, piperidine, morpholine, 7-methoxy-npropylamine, 7-isopropoxy «n ~ propylamine, Ν, Ν-diethylethylenediamine, Water, methanol, ethanol, propanol, isopropanol, n-butyl alcohol, aminoethanol, 4-aminoacetanilide, 2-mercaptoethanol, Phenol, thiophenol, 2-mercaptobenzothiazole, 2-mercaptonaphthalene, 2-aminobenzoic acid, 2-aminonaphthalene-6-sulfonic acid, 2-mercaptobenzoic acid, potassium cyanide, ck-naphthol, .ß-naphthol, benzyl alcohol, ρ-toluenesulfinic acid sodium, Sodium sulfite, calcium sulfite, etc.

Among the compounds of the formula (I) according to the invention are, inter alia, those which have a substituent X Contain the remainder of the amino or thiol groups of nitrogen-containing fibers, such as synthetic polyamides or Wool, or cellulosic with the hydroxyl groups

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Materials like cotton can react, and thus show the property of fiber reactivity. Such radicals X, which are used to react with the functional groups mentioned the polyamide and cellulose fibers are particularly suitable Sulfonic acid groups, alkyl and arylsulfonyl groups. such as the tosyl group, the cyano and the 2-mercaptobenzothiazolyl group.

The preparation of the complex compounds according to the invention takes place by reacting azo compounds of the type described with metal donors in the Way that metal complexes are formed that contain one or half an atom of metal in complex per molecule of azo compound Binding included. Accordingly, the metallization is expediently carried out with such metal-releasing agents and afterwards such methods, which experience has shown to provide complex compounds of this composition.

The preparation of 1: 2 complexes can be carried out in a single reaction step by converting 1 mole of a Heavy metal donating compounds with 2 moles of the corresponding azo compound or done in stages. In the latter In this case, a corresponding azo compound, for example one of the formula (3), is treated with a metal donating agent to a 1: 1 complex, and this subsequently with an equivalent amount of a corresponding metal-free azo compound converted to the 1: 2 complex.

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Al

This procedure is particularly recommended when 1: 2 complexes are prepared with dissimilar ligands Should be. Such 1: 2 complexes in which only one of the two ligands is a compound of the formula (I) can also by reacting an azo compound that is not a halogen-2,2-dihydroxypyridine Contains as a coupling component, with a chromium donating agent and subsequent reaction of the 1: 1 complex obtained with a corresponding azo compound of the formula (I) into the desired 1: 2 complex be transferred.

Instead of a 1: 1 complex compound with a suitable second component, as described above, im

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man /

To implement molar ratio 1: 1, can / can also be used as starting materials used non-metallized azo compounds in a molar ratio of 1: 1 in a mixed solution at the same time with a metal-releasing agent, so-called mixed metallization.

The reaction with the heavy metal-releasing agent takes place by customary methods, depending on the solubility of the components in various solvents, such as, for example, water, ethanol, formamide, glycol ether, pyridine. inter alia, if necessary at elevated temperature, in a weakly acidic to alkaline medium.
•. The implementation takes place advantageously in the heat,

open or under pressure - if necessary in the presence of suitable ones Additives such as salts of organic acids, bases or others that promote complex formation Means. '■ "

Particularly valuable complex compounds are

/ Salts as

obtained by using copper (II) - * nickel (II) or cobalt (II metal donors used.

As a copper-releasing agent, e.g. salts can be used which contain the copper as a cation, such as e.g. copper sulfate, cupifer acetate. In some cases it is the use of complex copper connections is an advantage.,

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e.g. in the form of copper-ammine complexes, such as copper tetrammine sulfate from copper sulfate and ammonia., pyridine or monoethanolamine, or in the form of compounds, which contain the copper in a complex bond, e.g. complex copper compounds of the alkali salts more aliphatic Aminocarboxylic acids, hydroxycarboxylic acids or dicarboxylic acids, such as glycocolla, glycolic acid, lactic acid, the Oxalic acid and especially tartaric acid, such as sodium copper tartrate, are aliphatic Tricarboxylic acids such as citric acid or aromatic oxycarboxylic acids such as SLicylic acid.

The treatment with the copper-releasing agent can be carried out by methods known per se, for example at room temperature if easily metallizable starting compounds are present, or by heating to temperatures between 50 and 120 ° in an open vessel, for example under reflux cooling or optionally in a closed vessel under pressure, whereby the p _TT ratios by the nature of the

ri

chosen metallization process are given; E.g. an acidic copper plating with copper sulfate, an alkaline one '' Copper plating with copper tetrammine sulfate. If necessary can also use solvents such as

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e.g. alcohol, dimethylformamide, etc. can be added.

The same applies to treatment with nickel-releasing or cobalt-releasing agents.

In the conversion into the metal complexes, a uniform azo compound is preferably used as the starting substance.

The azo compounds of the formula (6) or the heavy metal complexes concerned are prepared by coupling a diazotized amine of the formula D-NH _p with a halo-2,3-dihydroxypyridine and optionally subsequent reaction of the azo compound with a heavy metal-releasing agent.

The amine is diazotized by methods known per se, e.g. with the aid of hydrochloric acid and Sodium nitrite. The coupling with the halo-2,3-dihydroxypyridine also takes place according to methods known per se in acidic to alkaline medium.

After the coupling reaction has ended, the compounds can be metallized from the coupling mixture Be separated by filtration. They are expediently used as filter cakes without intermediate drying. In some In cases it is also possible to use the treatment

metal-releasing agents to be carried out directly in the coupling mixture without intermediate deposition.

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The treatment with the chromium or cobalt donating agents takes place according to the present method in in such a way that optionally with elimination of the alkyl radical an alkoxy group possibly in the o-position to the azo group a chromium or cobalt-containing compound is created, which pro

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Molecule of azo compound one or half an atom of chromium or half an atom /
/ Contains cobalt in a complex bond. Accordingly, the metallization is expediently carried out with such chromium- or cobalt-releasing agents and by methods which, experience has shown, give complex compounds of this composition. It is generally advisable to use one or less than one atom of chromium or cobalt for a molecule of an azo dye and / or to carry out the metallization in a weakly acidic to alkaline medium, optionally in the presence of organic solvents. Accordingly, those metal compounds that are stable in alkaline agents are particularly well suited for carrying out the process, such as complex chromium or cobalt compounds of aliphatic dicarboxylic acids or oxycarboxylic acids, such as oxalic acid, lactic acid, citric acid and especially tartaric acid, or complex chromium compounds of aromatic oxycarboxylic acids, such as salicylic acid. As cobalt-releasing agent, simple compounds of divalent cobalt, such as cobalt sulfate or acetate or, if appropriate, freshly precipitated cobalt hydroxide, can also be used with advantage in the present process.

The conversion of the azo compounds of the formula (1) into the complex metal compounds takes place with advantage in the heat, open or under pressure, possibly in the presence

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suitable additives, e.g. in the presence of salts of organic acids, bases, organic solvents or others the complex formation and / or the cleavage of the alkyl radical · der possibly in ο-position to the azo group Alkoxy group promoting agents.

Instead of starting from ο, ο'-dioxyazo compounds, one can also use the corresponding o-alkoxy-o ¹ -oxyazo compounds; the alkyl group of the o-alkoxy radical is split off during the metallization and the same metal complexes are obtained as from the dioxyazo compounds.

A particular embodiment of the present process is characterized in that one of mixtures various metallizable azo compounds that correspond to the general definition mentioned at the beginning, or at least one of which corresponds to this definition. the Treatment with the chromium or kobait-releasing agents also carried out here in the manner that chromium- or cobalt-containing complexes are formed, the azo compound per molecule

half an atom / one or half an atom of chromium ore / cobalt in complex

Binding included.

The cobalt and chromium compounds of this type which ^{contain two o, o 1} -dioxymonoazo compounds corresponding to the general formula (1), which both have the same composition, are valuable.

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The diazo components can be further substituted be, e.g. by chlorine or bromine atoms, nitro, cyano-lower Alkyl, preferably methyl, lower alkoxy, preferably methoxy, lower alkyl sulfonyl, such as methylsulfonyl and ethylsulfonyl, sulfonic acid, carboxylic acid, Sulfonamide and substituted sulfonamide, e.g. N-lower Alkylsulfonamide and N-lower hydroxyalkylsulfonamide-> e.g. N-methylsulphonamide, Ν, Ν-diethylsulphonamide, N- (ß-hydroxyethyl) -sulphonamide- and N, N-di (ß-hydroxyethyl) sulfonamide, substituted or unsubstituted phenylazo or naphthylazo, acylamino, such as formylamino, acetylamino, Benzoylamino, benzenesulfonamide, p-toluenesulfonylamino, Methanesulfonylamino-, Carbomethoxyamino- ,, Carboäthoxyarnino-, Dimethylaminosulfonylamino, carboisopropoxyamino groups, as well as reactive groups.

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The diazo compounds of the following amines may be mentioned as diazo components which can be used for the preparation of the compounds of the formula (6) according to the invention or the corresponding heavy metal complexes: aminobenzenes
1-amino-4-chlorobenzene,
1-amino-4-bromobenzene,

l-amino-4-methylbenzene.,. ,

l-amino-4-nitrobenzene, l-amino-4-cyanobenzene, 1-amino-2,5-dicyanobenzene, 1-amine-4-methylsulfonylbenzene, 1-amino-4-carbalkoxybenzene, 1-amino-2, K - dichlorobenzene, 1-amino-2,4-dibromobenzene, 1-amino-2-methyl-4-chlorobenzene, 1-amino-2-trifluoromethyl-4-chlorobenzene, 1-amino-2-cyano-4-chlorobenzene, 1-amino-2-carbomethoxy-4-chlorobenzene, 1-amino-2-carbomethoxy-4-nitrobenzene, 1-amino-2-chloro-4-cyanobenzene, 1-amino-2-chloro-4-nitrobenzene, 1- Amino-2 ~ bromo-4-nitrobenzene, 1-amino-2-chloro-4-carbethoxybenzene,

^ -methylsulfonylbenzene,

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as

1-Amino-2-methylsulfonyl-4-chlorobenzene, 1-amino -2, 4 -dini tro -6 -methyl sulphonyl benzene, l-amino-2,4-dinitro-6- (2'-hydroxyethylsulfonyl) - benzene, l-amino-2,4-dinitro-6- (2 ^! -chloroethylsulfonyl) -benzene, 1-amino-2-methylsulfonyl-4-nitrobenzene, l-amino-4-methylsulfonyl-2-nitrobenzene, 1-amino -2,4-dinitrobenzene, 1-amino-2,4-dicyanobenzene, 1-amino-2-cyano-4-methylsulfonylbenzene, 1-amino-2,6-dichloro-4-cyanobenzene, 1-amino-2,6 -Dichlor-4-nitrobenzene, l-amino-2,4-dicyano-6-chlorobenzene, 4-aminobenzoic acid cyclohexyl ester, l-amino-2,4-dinitro-6-chlorobenzene and in particular 1-amino-2-cyano 4-nitrobenzene,

l-aminobenzene-2-, -3- or -4-sulfonic acid amides, such as that N-methyl or N, N-dimethyl or diethyl amide, 2-aminonaphthalene-6-sulfonic acid-N, 7-isopropyloxypropylamide, l ~ aminobenzene-2-, -3- or ^ -sulfonic acid-Nj ^ -isopropyloxypropylamide,

1-aminobenzene-2-, -3- or -4-sulfonic acid-N-isopropylamide. l-aminobenzene-2-, -3- or -4-sulfonic acid-N, γ-methoxypropylamic. l-aminobenzene-2-, -3- or -4-sulfonic acid-N, N-bis- (ß-hydroxyethyl) -amide,
l-amino-4-chlorobenzene-2-sulfonic acid amide,

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and the N-substituted derivatives, '4-aminoazobenzene,
3,2'-dimethyl-4-aminoazobenzene, 2-methyl-5-methoxy-4-aminoazobenzene, 4-amino-2-nitroazobenzene, 2,5 ~ dimethoxy-4-aminoazobenzene, 4 ^! -Methoxy-4-aminoazobenzene, 2-methyl-4'-methoxy-4-aininoazobenzene, 3,6,4'-trimethoxy - ^ - aminoazobenzene, 4 '-ChIOr- ¹ I-aminoazobenzene, 2'- or 3'- Chloro-4-aminoazobenzene, 3 ~ nitro- ^! } - amino-2 ¹ , 4 '-dichlorazobenzene, ^ -aminoazobenzo.l- ^' -sulfonamide, 1- or 2-aminonaphthalene,

6-acetylamino - ² I-chloro-2-aminophenol, 6-nitro-4-chloro-2-aminophenol, 6-nitro-4-methyl-2-aminophenol, 3-amino-4-hydroxy-acetophenone, 6 -Nitro -K -acetylamino-2-aminophenol, S-nitro ^ -amino - ^ - hydroxy-acetophenone, 2-aminophenol -h -carboxamide, 4,6-dichloro-2-aminophenol, 3,4,6-trichloro- 2-aminophenol, 4-nitro-6-chloro-2-aminophenol,

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6-nitro- or o-chloro ^ -aminophenol ^ -sulfonic acid amide, 4-nitro-2-aminophenol-5- or -β-sulfonic acid amide, 2-aminophenol-5-methylsulfone.
2-aminophenol,

4- or 5-nitro-2-aminophenol, 4- or 5-chloro-2-aminophehol, 4,5-dichloro-2-aminophenol, 4-chloro-5-nitro-2-aminophenol, 2-aminophenol-4 - or -5-sulfonic acid, 3j 4j6-trichloraminophenol , 4-chloro-2-aminophenol-6-sulfonic acid, 6-chloro-2-aminophenol-4-sulfonic acids, 4-nitro-2-aminophenol-6-sulfonic acid, 6-nitro -2-aminophenol-4-sulfonic acid, 2 ~ aminophenol-4,6-disulfonic acid, 4,6-binitro-2-aminophenol , 6-acetylamino-2-aminophenol-4-sulfonic acid, 4-acetylamino-2-aminophenol-β sulfonic acid, 4-methyl-2-aminophenol, 4-methoxy-2-aminophenol, 2-aminophenol-4-sulfonamide, 2-aminophenol-4-sulfone-N-ß-hydroxyethylamide, 2-aminophenol-4-sulfone-N - methylamide, 2-aminophenol-5-sulfonamide, 4-chloro-2-aminophenol ~ 5- or -6-glyphonamide,

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2-aminophenol-4-sulfone-N, N-dimethylamide, 2-aminophenol-4-methylsulfone, 2-aminophenol-4-ethylsulfone , o-acetylamino - ^ - nitro ^ -aminophenolj 2-aminophenol-4, β-hydroxyethylsulfone , Anthranilic acid,

2-amino-3-naphthoic acid, 4- or 5-chloroanthranilic acid, 4- or 5-nitroanthranilic acid, 4- or 5-acetylaminoanthranilic acid, 4- or 5-sulfoanthranilic acid, anthranilic acid-4-sulfonamide,

Anthranilic acid-4- or -5, β-hydroxyethyl sulfone,

Anthranilic acid 4- or -5-ethyl sulfone,

^ l -Chlor-2 -aminophenol -5-sul fonsäure -N -me thylainid,

4- or 5 ~ benzoylaminoanthranilic acid, 2-anisidine,

4- or 5-chloro-2-anisidine, 4 ^ or 5 ~ nitro-2-anisidine, 2-anisidine-4- or -5-sulfonic acid, 2-methoxy-5-methylaniline, 2,5-dimethoxyaniline, 2-anisidine-4- or -5-ß-hydroxyethyl sulfone, 2-amino-1-naphthol-4,8-disulfonic acid, l-amino-2-naphthol-4-sulfonic acid,

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l-Amino-2-naphthol-4-sulfonamide, 6-nitro-1-amino-2-naphthol-4-sulfonic acid, 6-acetylamino-1-amino-2-naphthol-4-sulfonic acids 4- (2 ', 5 '-Disulfophenylazo) -2-methoxy-5-methylaniline, 4- (2 ^f , 5'-disulfophenylazo) -2,5-dimethoxyaniline, 4- (2 *, 5' -Disulfophenylazo) ^ -methoxy-l-naphthylamino- osulfonic acid,

4 ~ (1 ', 5'-disulfonaphth-2 ¹ -ylazo) -2,5-dimethoxyaniline, 4- (2', 3'- or 4 ¹ -sulfophenylazo) -2-methoxyaniline, dianisidine, ·

Benzidine ~ 3j3 ¹ -dicarboxylic acid,

4- (2'-, 3'- or 4 ¹ -sulfophenylazo) -2-methoxy-5-methylaniline,

4- (2'-, 3'- or 4'-sulfophenylazo) -2,5-dimethoxyaniline, 4- (2 ', 5'- or 3', 5'-disulfophenylazo) -2-methoxyaniline, 4- (3 'i5'-Disulfophenylazo) -2-methoxy-5-niethylaniline _J 4- (3', 5'-Disulfophenylazo) -2,5-dimethoxyaniline,

4- (2 * -carboxy-4 ¹ - or -5 ¹ -sulfophenylazo) -2-methoxyaniline, 4- (2'-carboxy-4- or -5'-sulfophenylazo) -2,5-dimethoxyaniline, 4- ( 2'-carboxy- ^{4'- or -5 1} -sulfophenylazo) -2-methoxy-5-methyl-

aniline,

4- (6 ^f > 8 ^f -Disulfonaphth-2 ^f -ylazo) -2-methoxyaniline, 4- (6 ', 8'-disulfonaphth-2 ^f -ylazo) -2-methoxyaniline,

4- (6 ', S ¹ -disulfonaphth-2 ^! -Ylazo) -2-methoxy-5-methoxyaniline,

4- (6 ', 8'-disulfonaphth-2'-ylazo) -2,5-dimethoxyaniline,

4-phenylazo-2-aminophenol,
2- (N, N-dimethylsulfonylamino) aniline, 2- (H, N-ditosylamino) aniline.

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• The azo compounds already mentioned 'which do not correspond to the formula (I) and which are optionally present in 1: 2 complexes as.Liganden in addition to an azo compound of the formula (1) can also differ from the above-mentioned diazo components as well as the derive the following coupling components:
Phenols, such as p-cresol,
3,4-dimethylphenol,
2,4-dimethylphenol,

2- or 3-acetylamino-4-methylphenol, 4-t-butylphenol,

2-hydroxy-5j6,7j8-tetrahydronaphthalene, 2-hydroxy ~ 3-sulfonic acid-5i6,7i8-tetrahydronaphthalene, 2-carboethoxyamino-4-methylphenol,
Resorcinol, ■.

m-aminophenol, 2,4-dihydroxyacetophenone, 2,4-dihydroxyazobenzene,

2,4-dihydroxyazobenzene-2'- or 4'-sulfonic acid, 2, 4-dihydroxyazobenzene-2 ', 5'-disulfonic acid, • 2,4-dihydroxy-4' -nitroazobenzol,
2,2 ', 4-trihydroxyazobenzene-3' * 5'-disulfonic acid, 2,4-dihydroxy-4'- or -5 ¹ - (acetylamino) -azobenzene-2 ^! - sulfonic acid,
4- (2 ", 4" -dihydroxyphenylazo) -4'-nitrostilbene-2,2'-disulfonic acid;

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Naphthols, such as 2-naphthol, 1,3 ". Or 1,5 ~ dihydroxynaphthalene, 2-naphthol-6-sulfonic acid, 1,8-dihydroxynaphthalene-3. » 6-disulfanic acid,

1,3 ~ D ⁱ hydroxynaphthalene-5-j -6- or -7-sulfonic acid,

_l> 3 ~ dihydroxynaphthalene-5i7-disulfonic _J 2-naphthol-6-sulfonamide 2-naphthol-6-ß-hydroxyäthylsulfonj 1-amino-7-naphthol,

1-acetylamino-7-naphthol, 1-propionylamino-7-naphthol, 1-carbomethoxyamino-7-naphthol, 1-carboethoxyamino-7-naphthol, 1-carbopropoxy-amino-7-naphthol, 1-dimethylaminosulfonyl-amino-7- naphthol , 2-amino-5-naphthol-7-sulfonic acid _f 2- amino-5-naphthol-1,7-disulfonic acid, 1-amino-4-naphthol,

2-amino-6-naphthol,

2-amino-6-naphthol-8-sulfonic acid,

2-acetylamino-5-naphthol-7-sulfonic acid, 2-benzoylamino-5-naphthol-7-sulfonic acid, 2-phenylamino-5-naphthol-7-sulfonic acid, 2- (3'-SuIfoanilino) -5-naphthol-7-sulfonic acid, 2-amino-8-naphthol-6-sulfonic acid, 2-acetylamino-8-naphthol-6-sulfonic acid,

209832/1146

2- (3'- or 4'-aminobenzoylamino) -5-naphthol-7-sulfonic acid, 2- (3'- or 4'-aminobenzoylamino) -8-naphthol-6-sulfonic acid, lr (3'- or 4 '-Aminobenzoylamino) -8-naphthol-3j6-disulphonic acid, 2- (3' ~ or 4'-aminoanilino) ^ -naphthol ^ -sulphonic acid, 2- (3 '~ or 4'-aminoanilino) -8-naphthol- 6-sulfonic acid, 1- (3 ^! - or 4'-aminoanilino) -8-naphthol-3, 6-disulfonic acid, 2- (3'-amino-4 ^1- sulfoanilino) -5-naphthol-7-sulfonic acids

2-phenylamino-8-naphthol-3 > 6-disulfonic acid,

2- (4'-Amino-3'-sulfoanilino) -5-naphthol-7-sulfonic acid, 2- (4'-Amino-3 ^1- sulfoanilino) -8-naphthol-6-sulfonic acid, l-amino-8 " naphthol-3j6-, -2,4- or -4,6-disulfonic acid,

1-Amino-8-naphthol-4-sulfonic acid, 1-phenylamino-8-naphthol-4-sulfonic acid, 1-amino-5-naphthol-7-sulfonic acid,

l-acetylamino ~ 8-naphthol-3,6- or -4,6-disulfonic acid, l-Benzoylamino-S-naphthol ^ jo'- or -4,6-disulfonic acid, l-phenylamino-8-naphthol-3i6- or -4.6-disulfonic acid,

1-naphthol-4-sulfonic acid,

l-naphthol-4,6-disulfonic acid, · ^!

2-naphthol-6,8-disulphonic acid, 1-naphthol ~ 5 ~ sulphonic acid, 2-naphthol ~ 3i6-disulphonic acid, 2-naphthol-3j6,8-trisulphonic acid, 2-amino-8-naphthol-3 > 6-disulphonic acid , 6 ~ acetyl-2-naphthol,

209832/1146

4-acetyl-2-naphthol, 4-methoxy-1-naphthol, 4-acetyl-1-naphthol, 1-naphthol-3-j -4- or -5 ~ ^su li ^> ° namid, 2-naphthol-3- , -4-, -5-, -6-, -7- or -8-sulfonamide, 5,8-dichloro-1-naphthol, 2-methylamino-5-naphthol-7-sulfonic acid, 2-methylamino-8- naphthol-6-sulfonic acid, 1-butylamino-8-naphthol-3i6-disulfonic acid, 1-naphthol-3,6,8-trisulfonic acid, 6-β-hydroxyethylsulfonyl-2-naphthol-3-sulfonic acid, 1-naphthol-3, 6- or. -3,8-disulfonic acid, 2- (4'-nitrophenylazo) -1-amino-8-naphthol-3,6- or -3,8-disulfonic acid,

2- (4'-nitrophenylazo ^ l-amino-S-naphthol ^ ö-disulfonic acid,

2- (2'- or 4'-sulfophenylazo) -lramino-8-naphthol-3 ^ 6-disulfonic acid, l ^ -Dichlor-S-naphthol, 1-naphthol-8-sulfonic acid, "

2- (2 ', 5'-disulfophenylazo) -l-amino-8-naphthol-3,6-disulfonic acid,

2-naphthol-7- or -8-sulfonic acid;

heterocyclic coupling components, such as barbituric acid, 2,6-dihydroxy ~ 3-cyano-4-methyl-pyridine; Pyridones, such as l-methyl-3-cyano-4-ethyl-6-hydroxypyridone,

l-Amino-J-cyano ^ -methyl-ö-hydroxy-pyridone,

1-phenyl-J-carbamido ^ -methyl-6-hydroxy-pyridone,

2,4-dihydroxyquinoline;

209832/1146

5-pyrazolones, such as

3 ~ methyl-5-pyrazolone,

1,3-dimethyl-5-pyrazolone, 5-pyrazolone-3-carboxylic acid and its amides, preferably 1-aryl-5-pyrazolones, such as 1-phenyl-3-methyl-5-pyrazolone,

l- (2'-, 3'- or 4'-methylphenyl) -3-methyl-5-pyrazolone, l- (2 ^f -, 3 'or 4'-SuIfophenyl) -3-methyl-5-pyrazolone, l- [3'- or 4 '- (β-Hydroxyäthylsulfonyl) -phenyl] -3-methyl-

5-pyrazolone,. .

1-phenyl ^ -earboxy ^ -pyrazolon, l- (3'- or 4'-aminophenyl) -3-methyl-5-pyrazolone, 1- (2'-methoxyphenyl) -3-methyl-5-pyrazolone,

l- (2 ^! -, 3'- or 4'-chlorophenyl) -3-methyl-5-pyrazolone,

1 - (3 '' - or 4'-aminophenyl) -3 ^"ca rboxy-5-pyrazolone,

l- (3'-Amino-4 ^f -sulfophenyl) -3- (carboxy- or methyl) -5-

pyrazolone,

l- (4 ^! -amino-3 ¹ -sulfophenyl) -3-carboxy- or methyl) -5-

pyrazolone,

1- (2 '~, 3'"or4'-nitrophenyl) -3-methyl-5-pyrazolone, 1- (2 ', 5'- or 3', 4'-dichlorophenyl) ~ 3-methyl-5- pyrazolone, l- (2 ', ^3? "or 4'-SuIfamylphenyl) -3-methyl-5" Py ^ aZOlOn ₅ I- (2',. 3' or 4'-methylsulfonylphenyl) -3 ~ raethyl -5-pyrazolone,

1-phenyl-5-pyrazolon-3 ~ carboxylic acid kresidid, 1-phenyl-5-pyrazolone-3-carboxylic acid-2'-toluidide ^,

209832 / 1Ui

1-phenyl-5-pyrazolone-3-carboxylic acid eanil id j,

l- (2'-, 3'- or 4 '-N-methylsulfamylphenyl) ~ 3-methyl - 5-

pyrazolone,

1- (6'-chloro-3 ¹ -methyl-4'-sulfophenyl) -3-methyl-5-pyrasolone, 1- (2 ^!, 5'-dichloro-4'-sulfophenyl) -3-methyl-5- pyrazolone,

1- (2 ^! -Methyl-5'-sulfophenyl) -3-methyl-5-pyrazolone, 1- (4'-chloro-2'-sulfophenyl) -3-methyl-5-pyrazolone.

l- (6'-chloro-4'-sulfo-2 ¹ -methylphenyl) -3-carboethoxy ~ 5-

p ^ razolon,

1- (2 ', 5' -disulfophenyl) -3-methyl- [5-pyrazolone, l- (4 '-Sulfophenyl) ^ -carboxy ^ -pyrazolon,

1- (2'-, 3 '~ or 4'-carboxyphenyl) -3-methyl-5-pyrazolone.

1- (6'-Chloro-4 ¹ -sulfo-2'-methylphenyl) -3 ~ methyl-5-pyrazolone

3 ~ carboxy-5-pyrazolone;

Acetoacetic acid amides, preferably acetoacetanilide and

Benzoylacetanilides, e.g.

Acetoacetanilide,

Acetoacet-4- (ß-hydroxyethylsulfonyl) anilide, Acetoacet-o-anisididj

Acetoacet-o-toluidide,

Acetoacet-o-chloranilide,

Acetoacetanilide-3- or -4-sulfonic acid, Acetoacet-3- or -4-aminoanilide, Acetoacet-rn-xylidide,

20983271146

Acetoacetanilide ~ 2-, -3- or -4-carboxylic acid, Benzoylacefcanilid, benzoyl-3- or -4-sulfonic acid, Benzcylacet-3- or -4-aminoaiiilid, acetoacetanilide -K -sulfonamides naphthylamines such as

2-naphthylamine, 1-naphthylamine, 1-naphthylamine-4-sulfonic acid , 2-methylaminonaphthalene, 2-aminonaphthalene-6-sulfonamide, 2-amino-8-naphthol-6-sulfonic acid, 2-methylamino-8-naphthol-6-sulfonic acid , 2-phenylamino-8-naphthol-β-sulfonic acid, 2-phenylaminonaphthalene, 2- (3'-chlorophenyl) -aminonaphthalene, 2- (2'-carboxyphenyl) -aminonaphthalenes, 2-aminonaphthalene-6-sulfonic acid, ^ -aminonaphthalene -ö-sulfonic acid-N-methylamide.

As examples of primary heterocyclic amines which can be used for the preparation of the azo compounds mentioned:

2-aminopyridine 2-aminochiriolin, 2-aminobenzothiazole,

2-amino-6-nitro-benzthiazolj, > Arnino-indazole, 209832/1146

^ -Aniino-o-chlorindazolj 5-amino-6-methoxy-indazolj 7-amino-indazolj

5-aminotriazole ~ 3-carboxylic acid ₃ .

3 ~ amino-4-phenyl ~ 5-methylpyrazole, 4-amino-benzotriazole, 7-amino-5-chlorobenzimidazole, 4-amino-5-chloro-benzothiazole 2-aminothiazole 2- amino- ¹ ! - methyl- thiazole,

5-amino-1 , 2, 4-triazole, l-phenyl-2,3-dimethyl-4 5-amino-2-phenyl-l ₃ ~ 5, 'i-thiadiazol., 5-amino-3-phenyl- l _J 2, ^ f-thiadiazole, 8-amino quinoline, 8-atiiinoquinoline-5-sulfonic acid, 5-chloro-8-aminequinoline _J 5-acetylamino-8-aminoquinoline _J 2-methyl-8-aminoquinoline, ^ -aminoacridine, 1-aminocarbazole , S-amino-S-nitro-thiazole,

209832/1146

4-Amino-2-methyl-pyrazolone (5) j 5,7-dit> ^rome -8-arnino-quinolines 8-amino-5- (4'-sulfophenylazo) -quinolines

5- (2 ^I -Sulfo-5 ^l -ci _J ß-dibromproplonylamino-l ^t -phenylazo) -8-

amlnochinolirij

2-Arnlno-5-methylthio-l _ί ~ $ _} h- thiadiazole 2-Amiiio-5-ethylthio-lj5j ^ -thiadiazole 2-amino-5-phenylthio-lj J, 4 ~ thiadiazole 2-amino-5-cyelohexylthio- l _} 5,4-thiadiazole 2-amino-5-methylsulfonyl-le5e ¹ l-thiadiazole 2-amino-5-raethyl-le5i ^ -thiadiazole

2-Amino-5-acetylamino-le 3 ^ 4-thi adiazole 2-Amino-5-phenylsulfonyl-le3j4-thiadiazole 2-Amino-5-chloro-le3j4-thiadiazole 2-Amino-5-carboromethoxyethyl-le 3j 4-thiadiazole

5-amino-2j1-benzisothiazole 5-Amino-5-methyl-2el-benzisothiazole 5-Amino-4-ethyl-2el-benzisothiazole 5-Amino-4e7-dimethyl-2el-benzisothiazole 5-Amino-4-methoxy-2e! -Benzisothiazoles 5-Amino-5-j -6- or -7-chloro-2e! -Benzisothiazole

203632/1146

3-Amino-5,7-dichloro or -dibromo-2,1-benzisothiazole, 5-amino-4-j -ξ> ~, ~ 6 ~ or -7-bromo-2, 1-benzisothiazole, 5-amino -5- or -6-cyano-2, l ~ benzisothiazole, 5-amino-4 _J 6-dichloro-5-cyano-2 _i 1-benzisothiazole, 5-amino-7-chloro-5-cyano-2 _J l -benzisothiazole, 3-amino-5-chloro-7-cyano-2 _J 1-benzisothiazole, 5-amino - ^ - methyl-6-cyano-2,1-benzisothiazole, 5-amino- · ¹ ! · - , - 5 ~> -6- or ^-1 J- nitro-2,1-benzisothiazole,

-2 _i 1-benzisothiazole,

5-amino-5-nitro-7-brora-2 _i 1-benzisothiazole, 5-amino-5- (N-methyl-sulfonamido) -2., L-benzisothiazole _; , 5-Amino-5- (N, N-dimethylsulfonamido) -2 _i 1-benzisothiazole, 5-amino-5-methylsulfonyl-2,1-benzisothiazole.

Compounds of the formula (I) or the corresponding heavy metal complexes, one or more

Containing reactive groups can be prepared in this way

or coupling / are that one diazo component !! used that already contain reactive groups. In many cases, however, it is also possible to subsequently add reactive groups to the azo

209832/1146

to introduce connections. The introduction can take place after the coupling or after the metallization. Of special Those compounds are of interest which have a six-membered heterocyclic compound bonded via an amino group or contain an aliphatic reactive radical containing no more than three carbon atoms.

The reactive radical is preferably introduced by acylation of corresponding azo compounds,

, which has an acylatable amino group

contain, or corresponding slide components, except the amino group to be diazotized yet another acylatable amino group or a group which, for example, by Reduction or saponification can be converted into an acylatable amino group, such as the nitro group or the acetylamino group, contain.

As such, in particular heterocyclic Diazokornponenten containing a Aminoarylazogruppe, such as 5- (3 'amino ·'! '-Sulf ophenylazo) -8-amino ~ quinoline, 5 - (^ - Arnino-2 ^f -sulfophenylazo) -8-amino-quinoline or 5- (h '-amino-2', 5'-disulfophenylazo) ~ 8-amino-quinoline, which can be converted into reactive diazo components by acylation of the amino group attached to the phenyl radical.

209032/1146

As further starting compounds (diazo or coupling components), which, as described above, .for the Introduction of a reactive radical are suitable, e.g.

named: Diazo components:

l, 3-diaminobenzene-4-sulfonic acid, 1,4-diaminobenzene-2-sulfonic acid, 1,4-diaminobenzene-2,5- or -2,6-disulfonic acid.

l-amino-4-nitrobenzene, 1-amino-2-chloro-4-nitrobenzene,

209832/1146

- ■

• ta

6-acetylamino-4-chloro-2-aminophenols 6-nitro-4-methyl-2-aminophenolj 4-nitro-2-aminophenol-6-sulfonic acid,

ö-Acetylamino-1-amino ^ -naphthol - ^ - sulfonic acid and others, E.g. mentioned in the list of possible diazo components

Links;

Coupling components:

2-acetylamino-4-methylphenol, m-aminophenol,

2,4-dihydroxy-4'-nitroazobenzene, 1-amino ~ 7-naphthol,

2 -amino -5 -naphthol -7 -sulfonic acid, 2-acetylamino-5-naphthol-7-sulfonic acid,

1- (3'- or 4'-aminoanilino) -8-naphthol-3j6-disulfonic acid,

1- (V-Απύηο-3'-sulfophenyl) ^-3-me thyl-5-pyrazolone

and other compounds mentioned, for example, in the list of possible coupling components.

Other ligands corresponding to the azo compounds of the formula (I) or not of the formula (1) in 1: 2 heavy metal complexes, can be introduced into the reactive residues (i.e. after coupling or after metallization, see above), e.g. the coupling products of the above-mentioned diazo or coupling components, with corresponding couplable connections, are given again contain acylatable amino groups, so that compounds of

209832/1146

Formula (1) or corresponding heavy metal complexes arise, which contain more than one reactive group in the finished molecule or complex.

. As acylating agents, apart from the acylating agents Place still contain a reactive radical, come in particular the halides or anhydrides of organic acids which contain easily exchangeable atoms or groups of atoms.

Acylating agents containing a fiber-reactive radical include, for example, the following: chlorine or bromoacetyl chloride,
ß ~ chloro- or ß-bromopropionyl chloride, α, β-dichloro- or α, ß-dibromopropionyl chloride, chloromaleic anhydride,
CarbyIsulfate,
Acrylic chloride,

β-chloro- or β-bromoacrylic chloride, α-chlorine or α-bromoacrylic chloride, α, β-dichloro or dibromoacrylic chloride, trichloroacrylic chloride, Chlorocrotonyl chloride, propiolic acid chloride,

3.5 "dinitro-4-chlorobenzene sulfonic acid or carboxylic acid chloride,

3 ~ Nitro-4-chlorobenzene sulfonic acid or carboxylic acid chloride, 2,2,3 »3" "tetrafluorocyclobutane-1-carboxylic acid chloride,

209832/1 U6

β-chloroethylsulfonyl-endomethylene-cyclohexanecarboxylic acid chloride.

Acrylsulfonyl-endomethylene-cyclohexanecarboxylic acid chloride, and especially heterocyclic acid halides and their

Derivatives like the

2-chlorobenzoxazole carboxylic acid chlorides,

2-Chlorbenzthiazolcarbori- or -sulfonsäurechloride and especially the following, at least 2 nitrogen atoms as heteroatoms of a 6-membered heterocycle onv. ^r iron

Links:

^, ^ - dichloro-l-phenylpyridazone carbon or sulfonic acid chloride,

4,5-dichloropyridazonopropionic acid chloride,

!, ^ - dichlorophthalazine carbon or sulfonic acid chloride, 2,3-dichloroquinoxaline carbon or sulfonic acid chloride, 2,4-dichloroquinazoline carbon or sulfonic acid chloride _> .

2-J-methanesulfonyl-4-chloro-6-methylpyrimidine, Tetrachloropyridazine,

2, ⁱ i - bis-rncthanesulfonyl-6-methylpyrimidine, 2,4,6-tri- or 2,4,5,6-tetrachloropyrimidine, 2,4,6-tri- or 2,4,5,6 -Tetrabromopyrimidine, 2-methanesulfonyl-4,5-dichloro-6-methylpyrimidine, 2, ^ - dichloropyrimidine-5-sulforic acid, 5-nitro- or 5-cyano-2,4, .6-trichloropyrimidine 2,6-Bif; -methanesulfonylpyridine-4-carboxylic acid chloride _i 2, ⁱ J-dichloro-5-chloromethyl-6-methyl-pyrimidine _i 2, K -dibromo-5-bromomethyl-6-methyl-pyrimidine,

209832/1148

2 _i 4-dichloro-5-chloromethylpyrimidine _J 2 _jr 4-dibromo-5-bromomethylpyrimidine, 2i5i6-trichloro-4-methylpyrimidine,

2 _J 6-dichloro-4-trichloromethylpyrimidine or in particular

2,4 ~ dimethanesulfonyl-5-chloro-6-methylpyrimidine, 2,4,6-trimethanesulfonyl-1,3,5-triazine, 2., 4-dichloropyrimidine., 3,6-dichloropyridazine, 3,6-dichloropyridazine-5-carboxylic acid chloride,

2,6-dichloro- or 2j6-dibromo- K -carboathoxypyrimidine,

2, ¹ 1, 5 -trichloropyrimidine, 2 _J 4-dichloropyrimidine-6-carboxylic acid chloride _i 2 _> 4-dichloropyrimidine-5-carboxylic acid chloride _J

2,6-dichloro- or 2 _{J-dibromopyrimidine} 6-4- or -5-carboxylic

acid amides or sulfonic acid amides or -4- or -5-sulfonic acid chloride, 2,4 , 5,6-tetrachloropyridazine,

^ -Nitro-ö-methyl ^ j ^ -dichloropyrimidine, 2-chlorobenzothiazole-6-carboxylic acid chloride _J 2-chlorobehzthiazole-6-sulfonic acid chloride,

S-nitro-ö-methyl-a ^ -dichloropyrimidine,

2,4,6-trichloro-5-chloropyrimidine,

2, h, 5 , 6-tetrafluoropyrimidine, h, 6-difluoro-5-chloropyrimidine,

py, 209832 / 1U6

2,4,5-trifluoropyrimidine,

2,4,6-Trichior- (-tribromo- or -trifluoro) -1,3j5-triazine, as well as 4,6-dichloro (dibromo or difluoro) -1,3., 5-triazines, which in 2-position are substituted by an aryl or alkyl radical, e.g. a phenyl, methyl or ethyl radical, or by the Remainder of an aliphatic or aromatic mercapto bonded via the sulfur atom or via the oxygen atom bonded hydroxyl compound or in particular by an NHp group or by the remainder of a via the nitrogen atom bound aliphatic, heterocyclic or aromatic amino compound. As such compounds, their remnants through Reaction with trihalotriazines in the 2-position can be bonded to the triazine nucleus, the following may be mentioned, for example: aliphatic or aromatic mercapto or hydroxy compounds, such as thio alcohols, thioglycolic acid, thiophenols, alkoxyalkanols, methyl, ethyl, isopropyl alcohol, glycolic acid, Phenol, chloro- or nitrophenols, phenolic carboxylic and sulphonic acids, naphthols, naphtholsulphonic acids, etc., in particular but compounds containing ammonia and aylable amino groups, such as hydroxylamine, hydrazine, phenylhydrazine, Phenylhydrazine sulfonic acids, glycol monoalkyl ethers, methyl, ethyl, isopropyl, methoxyethyl, methoxypropyl amine, Dimethyl, diethyl, methylphenyl, ethylene phenylamine, chloroethylamine, Ethane amine, propanolamine, benzylamine, cyclohexylamine, Morpholine, piperidine, piperazine, aminocarbonic acid ester, Aminoacetic acid ethyl ester, aminoethane sulfonic acid,

209832 / 1U6

N-methylaminoethanesulfonic acid, but especially aromatic amines such as aniline, N-methylaniline, toluidines, xylidines, chloroanilines, p- or m-aminoacetanilide, aminophenols, anisidine, phenetidine and, in particular, anilines containing acidic groups, sulfanilic, methanilic, orthanilic acid , Anilinedisulfonic acid, aminobenzy] sulfonic acid, aniline-ou-methanesulfonic acid, aminobenzenedicarboxylic acids, naphthylaminomono-, di- and trisulfonic acids, aminobenzoic acids, such as 2-hydroxy-5-aminobenzoic acid, and also colored compounds, bzv, ^T. Compounds with dye character, for example 4-nitro-V-aminostilbene disulfonic acid, 2 ~ nitro-V -amino-diphenylamino-4, 3 '~ stilbene-disulfonic acid, 2-nitro-4'-aminodiphenylamine-4,3 ¹ "disulfonic acid and in particular aminoazo dyes or aminoanthraquinones or phthalocyanines which still contain at least one reactive amino group.

The introduction of the 2-position of the triazine residue standing substituents can also after the condensation with the starting diamine or after the reaction according to the invention to the azo compound of the formula (I) happen.

Except for those which can be introduced by acylation, as fiber-reactive residues also mentioned, e.g. the vinyl sulfone, the ß-sulfato- or -thiosulfatoethylsulfon-, ß-thiosulfatopropionylamide-, the ß-Thiosulfatoäthylsulfonylamid- or the Sulfonic acid-Njß-aulfatoäthylamidgruppe, which in another way, be introduced into the diazo component e.g. by ester or thioester formation οη9832 / 11 £ 6

As compounds that contain a fiber reactive radical that cannot be introduced by acylation, in which the fiber · reactiveresf therefore preferably not via an amino group but is directly bound to the benzene residue, the sulfoesters of the following sulfones should be mentioned in particular: l-Amino-2-methoxy ~ 5- (ß-hydroxyethyl) -phenylsulfone, l-aminobenzene-3- or -4-ß-hydroxyethylsulfone, l-amino-2-methyl-benzene-5-ß ~ hydroxyethyl sulfone, l-amino-4- (ß-hydroxyethylsulfonylpropionylarninomethyl) benzene, l-amino-4- (ß-hydroxyäthylsulfonylamino) benzene, as well as reactive compounds obtainable via corresponding methylols according to Einhorn, such as e.g. l-Amino - ^ - chloroacetylamino-methylbenzene or l-Amino-J-chloroacetylamino-methylbenzene-o-sulfonic acid.

The condensation with the acid halides or anhydrides or with the heterocyclic halogen compounds is conveniently carried out in the presence of acid-binding agents, such as sodium carbonate or sodium hydroxide, and under The conditions are such that the finished product still has a unsaturated bond or an exchangeable halogen atom remains, i.e. e.g. in organic solvents or at relatively low temperatures in an aqueous medium.

209832/1146

The 1 rl heavy metal complexes, especially the 1: 1 cobalt complexes of the azo compounds according to the invention can be caused by the addition of several, in particular three, organic residues that are attached to the Metal atom are bound, are stabilized.

Of the radicals which form a chelate complex with the metal via a primary, secondary or tertiary nitrogen atom, at least two, preferably all three, belong to one and the same, preferably aliphatic polyamine, with three or preferably two between the individual nitrogen atoms contains further atoms, so that the chelate complex or complexes formed, including the metal atom, are 6- or preferably 5-membered. Examples of such polyamines are: diaminoalkylenes, in which the alkylene bridge consists of J> or preferably 2 carbon atoms, or N-alkyl, N-aminoalkyl or C-aminoalkyl derivatives thereof, e.g. ethylenediamine, 1,2- or 1, jJ- Diaminopropane, 1,2- or lj> -diaminon-butane, ß- (methylamino) -ethylamine, ß- (ethylamino) -ethylamine, ß- (dirnethylamino) -äthvlamin, N- (ß-hydroxyethyl) -ethylenediamine, N, N '-Dirne t hy I ethylenediamine, Ν, Ν', Ν "-trimethylethylenediamine, !!, MSN", ^ "- tetrainethylethylenediamine, but especially diethylenetriamine, triethylenetetramine,

209832 / 1U6

Tetraethylene pentamine, dipropylene diamine etc.

If a diamine is used, comes third, ligand complexed to the metal atom ammonia or a primary, secondary or tertiary amine in question, e.g. Methylamine, ethylamine, mono- and diethanolamine, dimethylamine, Diethanolamine, benzylamine, aniline, triethanolamine, Piperidine or pyridine.

In the case of the cobalt complexes in particular, the new compounds are expediently prepared Metallization of the mixture of the azo compound and the amine or amines with cobalt donating agents, the Reaction is practically instantaneous. In the event that there is an alkoxy group adjacent to the azo group, this is converted into a hydroxyl group in the usual way during the metallization (intermediate) (so-called dealkylating Metallization). You can also first by reacting the amines mentioned with cobalt-releasing agents

209832/114 6

prepare the corresponding 1: 2 cobalt amine complexes and then convert them into the complexes by reaction with a metalizable azo compound. In case of Chromium complexes can be produced conveniently in the V / eise, that you first use the 1: 1 chromium complex Produces azo compound and then reacts it with the amine or amines.

When carrying out the manufacturing process mentioned in the first place, it is generally advisable to the metallizing agent, the azo compound; and the amine or amines roughly in accordance with the composition the stoehiometric quantities required for the end product. to use. It is also generally recommended that the metallization be carried out in a weakly acidic to alkaline medium to execute. As cobalt donors are preferred uses simple cobalt salts, such as cobalt sulphate, or, if necessary, freshly precipitated cobalt hydroxide. With these simple With cobalt salts, the treatment according to the invention can also be carried out in a weakly acidic medium.

The transformation into "the complex cobalt compounds takes place with advantage in the warm, open or under pressure, e.g. at the boiling point of the reaction mixture, if necessary in the presence of suitable additives, e.g. in the presence of salts of organic acids,

209832 / 1U6

of bases, organic solvents, such as glycol monomethyl ether, Ethanol or N-butanol, or others., agents promoting complex formation.

Surprisingly, show these amine complexes in the azo compound v / eder sulphonated contain carboxyl groups., Not only an excellent _alcohol} but partly also a good water solubility.

209832/1146

The metal-containing, in particular copper- or nickel-containing azo compounds are new; they are suitable for dyeing and printing a wide variety of fabrics but especially for dyeing animal materials, such as silk, Leather and especially wool, but also for dyeing and printing synthetic fibers made from super polyamides or super polyurethanes, polyacrylonitrile fibers and the like.

If no sulfonic acid groups or the like are present, the water-solubility of the metal complex compounds according to the invention is important greatly reduced. Instead, the result is a far better solubility in organic solvents. If there are no solvatable substituents, e.g. a sulfonamide or nitro group is present, the solubility is only moderately in organic solvents.

The complexes with one or more sulfonic acid groups are particularly suitable as dyes for wool, Silk, leather and especially polyamides. The ones containing sulfonamide groups Complexes can be used as varnish dyes and as dyes for dyeing polyamides spinning mass. If the complexes that have a fiber-reactive group contain two or more sulfonic acid groups, see above

209832 / 1U6

they can be used as usual as reactive dyes will; if sulfonic acid groups are completely absent, lie reactive disperse dyes.

The heavy metal complexes according to the invention, the obtained a cationic charge are particularly useful as dyes for polyacrylonitrile fibers.

The new dyes can be used to dye nitrogen-containing fibers such as wool, e.g. from acetic to neutral Bathing, if necessary, i.e. when using only limited water soluble. Dyes with the addition of suitable dispersants, be used. In particular when using readily water-soluble, i.e. two or more in the azo compound Complexes containing sulfo groups are useful under Addition of the auxiliaries customary in dyeing, colored.

Furthermore, nitrogen-containing fibers, in particular wool, can be produced using the present process Dyes are colored in an advantageous manner, if one, expediently in a continuous procedure, e.g. on the padder to which an aqueous preparation is applied. Which contains a wool dye and an auxiliary that is able to form a system of two liquid phases with a miscibility gap with water and optionally additives, wherein. the quantitative ratio between the water, which may contain additives, and the auxiliary within the mixing

209832 / 1U6

gap or is close to it, the miscibility gap is already present with a relatively low content of auxiliaries is and is inherently large in the miscibility gap the phase with more resources makes up an essential part, and that the material provided with the aqueous preparation is then subjected to a heat treatment.

The dyeings and prints available with the new dyes are usually characterized by uniformity, by acid and alkali resistance, by good lightfastness and by good rubfastness; they change their appearance on As a rule, there is hardly any artificial light and some of them show very interesting and four-full nuances.

Particularly pure nuances are obtained with the new 'dyes when dyeing polyamide fibers, especially when dyeing Coloring of nylon-6,6 material.

In the following examples the parts mean, unless otherwise indicated, parts by weight, the Percentages by weight and temperatures are given in degrees Celsius. Between parts by weight and parts by volume there is the same relationship as between grams and what

209832/1 U6

Example 1.

42.5 parts of the alkaline coupling of

2 _i 3-dihydroxy-5-t> rompyridine ^with diazotized 8-aminoquinoline-5-sulfonic acid obtainable monoazo dye are dissolved with stirring in 800 parts of water at a temperature of 80-90. After 11 parts of n-butylamine have been added dropwise, the reaction solution is stirred at 90-95 until no more unchanged initial color can be detected. The color of the solution changes from red-violet to orange-brown. For the separation of the new dye of the presumed formula

80 parts of sodium chloride are added to the reaction solution, the precipitated dye is isolated by filtration and washed with dilute sodium chloride solution.

. The dye paste obtained is mixed with parts of crystallized sodium acetate in 1000 parts of water dissolved at 70-75 ° with stirring. After adding a solution of 27.5 parts of crystallized copper sulfate in 200 parts of water the metallization mixture is stirred at 70-75 until the

208832/1146

metal-free starting dye can no longer be detected. The resulting blue 1: 1 copper complex the dye of the above constitution is separated from the solution by adding sodium chloride, filtered and mixed with Washed sodium chloride solution. The dye obtained after drying and grinding can be used to leach full or polyamide fibers dye from a weakly acidic bath in real, gray-blue tones.

If the dye is metallized with 30 parts of nickel sulfate heptahydrate or rather than copper sulfate. 15 parts of Kqbalt-II-sulfct-heptahydrate made so the corresponding 1: 1 nickel or 1: 2 cobalt complex is formed, Which wool or polyamide fibers from a weakly acidic bath are dyed in pure blue-green or green tones can.

The dye paste obtained according to the above procedure is made with 800 parts by volume Viasser, 25 parts by volume a 20pigen Sodium carbonate solution and 130 parts by volume of a 3 * 07 vol. £? Chromium-containing aqueous solution of sodium disalicylatochromate III stirred under reflux until the starting dye is no longer detectable. The addition of 1: 2 chromium complex precipitated and isolated by filtration with potassium chloride of the starting dyestuff dyes full in greenish gray tones.

209832 / 1U6

Example 2.

42.5 parts of the azo dye mentioned in Example 1 from diazotized 8-aminoquinoline-5-sulfonic acid and 2,3-dihydroxy-5-bromopyridine are 1000 parts Stirred water at room temperature. After 20 parts of anhydrous sodium sulfite have been introduced, the reaction mixture is stirred at 30 ° -35 ° for 12 hours. The original The suspension turns into a clear solution without changing the initially red-violet hue. The starting dye can no longer be proven. The new dye of the probable constitution

HO OH

-W = K- <f N HO S ^

is separated from the solution by adding ammonium sulfate, filtered off and washed with concentrated ammonium sulfate solution. The corresponding 1: 1 copper complex is obtained by metallizing with copper sulfate as described in Example 1 obtained that dyes full or polyamide fibers from a weakly acidic bath in pure blue tones.

The implementation can also be done with the 1: 1 copper complex of the starting dye can be carried out. The new complex

209832/1146

is identical to the above-described copper-containing dye obtained by subsequent metallization.

Example 3

38.0 parts of the alkaline coupling of 2, 5-dihydroxy-5-chloropyridine with diazotized 8-aminochincline-5-sulfonic acid available monoazo dye with 1000 Parts of water of 50 stirred. After adding 10 parts Sodium bicarbonate and 20 parts of sodium p-toluenesulfinate the reaction mixture is stirred at 50 for 24 hours. the end The originally clear solution crystallizes the new dye of the presumed constitution

CB ₅

largely off. Deposition vn'rd by adding potassium chloride completed, the dye isolated by filtration and with diluted Kai: 'u :: iclr er.i dl ϋ:. ;; ιη; - washed.

Will the received; ^Farl>:. Toffpai5t ^(j according to don ^ AIVN de ^1; BeiJ3] ii ( »] i / mi t copper, I, MCs; r1 cnh] Kob.-il 1.:-ul fat inotiä. 1 1 i-

209832 / 1U6

- 5fr-

the corresponding 1: l copper or nickel or 1: 2 cobalt complex, with which full or polyamide fibers can be colored in true blue-green to green tones.

Example 4.

42.45 parts of the monoazo dye accessible by alkaline coupling of 2,3-dihydroxy-5-bromopyridine with diazotized 4-chloro-2-aminophenol-6-sulfonic acid are dissolved in 800 parts of water at 80 ° with stirring. After 10 parts of piperidine have been added dropwise, the reaction mixture is stirred at 90-95 until the starting dye can no longer be detected. The color of the solution changes from purple to red-brown. The new dye of the presumed constitution

? ^H

HO ₃ O-

Cl

HO OH

H ₀ C CH ₀ 21 \ d

H ₀ C CH ₀ 2/2

is deposited by adding ammonium sulfate, isolated by filtration and treated with concentrated ammonium sulfate solution washed. The metallization with copper sulfate according to the information in Example I gives the corresponding, green-

209832/1146

blue 1: 1 copper complex, the full from weakly acidic bath colors in real tones.

Example 5.

42.5 parts of the monoazo dye mentioned in Example 1 crystallized from diazotized 8-aminoquinoline-5-sulfonic acid and 2, j5-dihydroxy-5-bromopyridine, 15 parts Sodium acetate and 20 parts of 4-aminoacetanilide stirred with 1000 parts of water at 90-95 ° until the starting dye is no longer detectable. The first The violet-red solution takes on a yellow-brown color. The new dye of the likely formula

HO OH N = N <^ N

NHCOCH

When the reaction solution cools, it partially precipitates and is completely separated off by adding sodium chloride. The dye paste obtained after filtering and washing with sodium chloride solution yields on metallization according to the specifications of the Example 1 the corresponding green-blue 1: 1 copper or blue-green 1: 1-nickel or green 1: 2 cobalt complex.

203832/1146

The dye paste obtained according to the above procedure is mixed with 500 parts by volume of a 10 ^ strength sodium hydroxide solution stirred and the resulting solution then stirred under reflux until the originally present acetylamino group is completely saponified to the free amino group. The reaction solution becomes cooled to 5 to 10 and neutralized by adding concentrated hydrochloric acid. After stirring in 17 parts Sodium hydrogen carbonate is the reaction solution with vigorous stirring with the solution of 27 * 5 parts of a ^ ß-dibromopropionic acid chloride added in 50 parts by volume of acetone and stirred at constant temperature until none free amino groups can be detected. The one α, ß-dibromopropionylamino group having new dye is according to the information in Example 1 in the corresponding 1: 2 cobalt complex transferred, which colors full in true blue-green tones.

The specified saponification and renewed acylation can also be carried out with the corresponding 1: 2 cobalt complex des acetyiamino group-containing starting dye carried out will.

209 832/1146

Example 6.

5 ^, 5 parts of the by alkaline coupling of diazotized 8-aminoquinoline with 2,5 ~ dihydroxy-5-bromopyridine The monoazo dye obtained is stirred at 100 parts by volume of glycol monomethyl ether. After dropping of 15 parts of 2-aminoethanol, the reaction mixture is stirred at 100 to 105 until the red-violet starting dye completely converted into the red-brown new dye of the following constitution is

The dye is precipitated by diluting the reaction mixture with water, isolated by filtration and im Vacuum dried at 80.

4O, 4 parts of the new dye are concentrated with stirring in 200 parts by volume. Sulfuric acid at 0 to dissolved. After stirring for several hours at the same temperature, the reaction mixture is poured onto ^ 00 parts of ice. The precipitated as a precipitate Sohwefelsaurehalbester of the above dye is abfiltriort and washed with dilute sodium chloride i dlosung. By metallizing the

P09832 / 1U6

Dye paste with copper, nickel or cobalt sulfate according to the information in Example 1 are the corresponding Metal complexes are obtained with which woolen knitting yarns are dyed in gray-blue or blue-green shades can.

209832/1146

Example 7 «

42.5 parts of the azo dye indicated in Example 1 are stirred with 800 parts of water at 80 °. After adding 30 parts of crystallized sodium acetate and 15 parts of 2-aminobenzoic acid, the reaction mixture is heated to boiling with stirring until the Starting dye can no longer be detected. The resulting orange-brown solution contains the dye of Formula

HO OH

N = N- ^ f __ N NH

HOOC

If the metallization of the reaction solution with copper, nickel or cobalt sulfate is carried out according to the information in the example undertaken, the corresponding metal complexes are formed, which are deposited and carried out by adding sodium chloride Filtration can be isolated. The new dyes are suitable for dyeing wool or polyamide fabrics in real gray-blue to blue-green colors.

209832/1146

Example 8.

3 ^ jO parts of the monoazo dye mentioned in Example 5 are stirred with 800 parts of water of 50 and 25 parts by volume of a 20 $ strength sodium carbonate solution. The deep 8.5 parts of 2-mercaptoethanol are added to the red-violet solution and then stirred at 65 to 70, until the starting dye is completely consumed. The yellow-brown reaction solution becomes the new dye of the ' presumed constitution

HIGH ₂ OH ₂ -S

precipitated by addition of sodium chloride, by filtration isolated and washed with dilute sodium chloride solution. The obtainable according to the information in Example 1 1: 1 nickel complex of the new dye dyes polyamide fibers in pure greenish shades of blue.

209832/1146

Example 9 »

42.5 parts of the monoazo dye indicated in Example 1 are mixed with 600 parts by volume of water of 90 and 50 parts by volume of a 20% sodium carbonate solution. After adding 10 parts of phenol, the reaction mixture is stirred under reflux until the originally red-violet color of the solution has changed to orange-yellow. The resulting new dye of the probable structural formula

HO OH

is converted into the corresponding 1: 1 metal complexes by metallizing with copper or nickel sulfate according to the instructions in Example 1 transferred which polyamide fibers dye in gray-violet or gray-blue shades.

209832/1148

Example 10.

51.0 parts of the alkaline coupling of 2,3-dihydroxy-5-bromopyridine obtained with diazotized 2-aminophenol Monoazo dye with 1000 parts by volume of water stirred by 80. After the addition of 15 parts of anhydrous neutral sodium sulfite, the reaction mixture becomes 12 hours stirred at 90. The new coloring matter of the constitution becomes from the violet-red solution

precipitated after clarification by the addition of potassium chloride and isolated by filtration. The one available in the usual way l: l copper complex dyes polyamide fibers in blue, the corresponding one 1: 1 nickel complex in purple tones. The 1: 2 cobalt complex provides blue-gray dyeings on woolen knitting yarn.

209832/11 AB

Example 11.

44.0 parts of the 1: 1 chromium complex obtainable in a known manner of the monoazo dye from diazotized 1-amino-2-hydroxynaphthalene-4-sulfonic acid and 2-hydroxynaphthalene and 41.7 parts of the monoazo dye obtainable according to Example 1 are with 1000 parts of water of 80 and 50 parts of a 20% sodium carbonate solution was stirred until homogeneous. Afterward the reaction mixture is stirred at 90 to 95 until the two starting dyes are no longer detected can be. The resulting deep blue solution contains the uniform mixed complex of the following constitution

The new dye dyes wool or polyamide fibers from a weakly acidic bath in full red-tinged blue tones.

209832/1148

6 *

Similar copper, nickel and cobalt complex dyes, which have the colors indicated in columns IV, V and VI of the table below can be obtained from the diazo and coupling components of columns I and II, the substituting components of column III and the corresponding metal-releasing compounds.

209832/1 US

ι
ι K>
CD 1 I.
Diazo component II
Clutch
component i III
substituting
component IV
1: 1 copper
complex V
1: 1 nickel
complex VI
1: 2 cobalt
complex 9832 2 8-aminoquinoline 2,3-dihydroxy
5-chloropyridine \ 7-methoxy-n-
propylamine blue green Blue blue green / 114 t! 2,3-dihydroxy
5-bromopyridine 7-isopropoxy
n-propylamine blue . green Blue . green ro !! » It 2-mercapto
benzoic acid green Blue blue green green 5 1! !! Ν, Ν-diethyl
ethylenediamine blue green Blue blue green i ^ 8-arr.inochinoline -
5-sulfonic acid 2., 3-dihydroxy
5-bromopyridine Thiophenol green Blue blue green I.
green 7th t! It 2-mercapto
benzthiazole gray-blue green Blue blue green i ³ ft dd Potassium cyanide blue green Blue blue green ; ⁹
! !! dd 2-aminonaphtha-
\ lin-6-sulfone-
acid gray-blue green Blue blue green ί
ί 3-amino-7-
chlorindazole I 2,3-dihydroxy
: 5-tiromopyridine I cyclohexylamine blue
violet violet
ι gray-blue 2-amino-4-
phonyl-1,5,5-
VA J.. · -. ' . < --- '/ j -J J_ ! It I 2-mercapto-
! naphthalene green Blue blue green
ί green

O CO O

Instructions for dyeing woolen fabrics.

In a dye bath made from 3OOO parts of water, 5 parts of 40% acetic acid, 10 parts of sodium sulfate, 2 parts of the Aethylenoxydanlagungsproduktes, the preparation of which is described below and 1 part of the example 1 consists of 1: 2 cobalt complex mentioned, is at a temperature of 50 to βθ with 100 parts of wool received. After the bath has been heated to a boil within half an hour, another ' Colored at boiling point for one hour. After rinsing and drying, the result is a uniform green-blue color. The production of the ethylene addition product can be done as follows:

100 parts techn. Oleylamine is mixed with 1 part of finely divided sodium and heated to 1 ^ 0, whereupon ethylene oxide is introduced at 155 to 140. As soon If the ethylene oxide is absorbed quickly, the reaction temperature is lowered to 120 to 125 and then the Introduction of the ethylene oxide continued until the absorption of ! I) Share Acthylerroxyd. The reaction product obtainable in this way is practically clearly soluble in water.

209832 / 1U6

Specification for dyeing polyamide.

In a dye bath., Which is made from 5000 parts of water, 5 parts of 40% acetic acid, 10 parts of sodium sulfate

i / ·

and 1 part of the copper complex mentioned in example / exists, is at a temperature of 50 to 60 with 100 parts nylon-6,6-gev / ebe were received. After within half an hour the bath was heated to boiling ^, another hour at boiling temperature colored. "After rinsing and drying, the result is a uniform gray-blue color.

209832/1146

Specification for dyeing woolen knitting yarn.

In a dye bath made from 3000 parts of water, 5. Parts of 40% acetic acid, 10 parts of sodium sulfate, 2 parts of the Aethylenoxydanlagerungsproduktes described in the preceding dye example for wool fabric and 1 part of the 1: 1 copper complex described in Example 2

ο is made at a temperature of 50 with 100 parts pre-wetted woolen knitting yarn. The bath is heated to the boil over the course of half an hour and this Temperature maintained for another hour. It is then rinsed and dried. There will be an even, obtained green-blue coloration of good fastness properties. With the corresponding 1: 2 cobalt complex also result uniform, blue-green dyeings of very good fastness properties.

By extracting the dyed wool fibers with a mixture of pyridine and water in a ratio of 1: 1 you can only Remove a small amount of dye, suggesting a covalent bond between the dye and the wool fiber, replacing the According to Example 2 introduced sulfonic acid group can close against suitable groups of the wool fiber.

Similar results are obtained when the 1: 2 cobalt complex mentioned in Example 3 is used as the dye will. The blue-green dyeings that can be achieved are also characterized by good wet fastness properties and resistance to Extraction by pyridine / water.

209 832/1146

Dyeing cotton:

2 parts of the 1: 1 cure complex described in Example 2 'and 2 parts of anhydrous sodium carbonate are in a mixture of 25 parts of urea and 75 parts of water / water dissolved at room temperature. A cotton fabric is impregnated with the solution obtained and squeezed to an increase in weight of 75% off, dries at 90 to 100 and then subjects the impregnated fabric to the action of dry heat of approx. 140 for 60 seconds. After rinsing and soapy, one obtains a flowery, reddish-tinged blue coloration, which compared to an extraction with a mixture of dimethylformamide and V.'asser is resistant in a ratio of 1: 1.

With the corresponding 1: 2 cobalt complex, under a strong greenish blue coloration with the same fastness behavior is achieved under the same conditions.

The dye given in Example 5 is also used as the dye 1: 2 cobalt complex is used, this also results a green-blue coloration which is excellent due to its high wet fastness and stability against extraction.

In the case of the colorations indicated above, there is a reaction of the dye with the fiber, i.e. replacement of the substituents introduced in Examples 2 and 5 by reactive ones Assume groupings of cellulose fiber.

209832/1 1 46

Claims (2)

Claims ♦ 1. Azo dyes as the remainder of the coupling component contain the remainder of a dihydroxypyridine to which a substituent is also attached in the o-position to the azo bridge, which contains at least one hetero atom, the substituent not being allowed to be a halogen atom. 2. Azo dyes according to claim 1, wherein the in the o-position substituent bound to the azo bridge is bound to the dihydroxypyridine radical by a heteroatom. 3. Azo dyes according to Claims 1 and 2, the formula HO OH (1) D-W = If- <T N wherein D is the radical of a diazo component and X is a substituent which contains at least one heteroatom, the Substituent may not be a halogen atom. K. Azo dyes according to claim 5 of the formula (I), in which X is a hydroxy, alkoxy, phenoxy, naphthoxy, mercapto, amino or sulfone group. 209832/1146 5 azo dyes according to claim 5 of the formula (I), wherein X is a water-solubilizing group, in particular one Is sulfonic acid group. 6. Azo dyes according to Claim 5 of the formula (I), wherein X is an amino group to which a fiber-reactive Substituent is bound. 7. Azo dyes according to Claim 3 of the formula HO OH (2) ■ ' _{N N} HO OH where D and D ¹ each represent the radical of a diazo component and R is the radical of a diamine. 8. Salts of dyes according to claims 1 to • 7 with higher molecular weight, preferably quaternized amines. 9. Heavy metal complexes that contain one or two molecules of azo compounds of the formula (I) on a metal atom. 209832/1 146 10. Heavy metal complexes which, in addition to an azo compound of the formula (I) contain another azo compound that does not the remainder of a 2,3-dihydroxypyridine as a coupling component having. 11. Heavy metal complexes of azo compounds of the formula (I) which contain one atom of cobalt, nickel or copper, 12. Azo compounds according to Claims 1 to 11, which contain a reactive radical. 15. Azo compounds according to claims 1 to 12, the contain a reactive radical in the diazo component. 14. Azo compounds according to claims 1-8, the one contain water-solubilizing group. 15. Heavy metal complexes of azo compounds according to Claims 1 to 3 * wherein the remainder of the diazo component is 5- or 6-membered heterocyclic radical. 16. Heavy metal complexes of azo compounds according to claim 5 ·. wherein the heterocyclic radical has two nitrogen atoms contains. 209832 / 1U6 17 · Heavy metal complexes of azo compounds according to claim J>, in which the heterocyclic radical contains a fused-on benzene radical. 18. Heavy metal complexes of azo compounds according to claims 1 to 17 > those of the formula HO OH D— ^ KT = If— \ N X
in which D is a quinoline bonded in the 8-position rest is. 19. Heavy metal complexes of azo compounds according to claims 1 to Ιδ. Which of the formula X correspond, where Z is a halogen atom, a sulfonic acid, Means acylamino or arylazo group. 20. Heavy metal complexes of azo compounds according to claims 1 to 19 * in which the complex-forming metal is copper or nickel. 209832/1 1 46 τ * 21. Azo dyes according to Claims 1 to 20, in which the substituent bound in o-position to the azo bridge the radical of a high polymer organic bonded via an oxygen or sulfur atom or an amino group Pulp is. 22. Process for the production of azo dyes, which contain the remainder of a dihydroxypyridine as the remainder of the coupling component, which are additionally in the o-position a substituent which contains at least one heteroatom is bonded to the azo bridge, the substituent may not be a halogen atom, characterized in that azo dyes, which are the remainder of the coupling component Contain the remainder of a dihydroxypyridine, to which a halogen atom is bonded in.o-position to the azo bridge, with substituting compounds which contain a corresponding radical, converts. 23. The method according to claim 22, characterized in that that one starts from substituting compounds, the remainder of which is connected to the dihydroxypyridine residue by a heteroatom is bound. . 24. The method according to claims 22 and 23, characterized characterized in that one compounds of the formula 209832/1 146 HO OH (6) D-N ^ - ^^ r where D is the remainder of a diazo component and Y is a halogen atom, reacts with substituting compounds, which contain a radical which contains at least one heteroatom, the radical not being allowed to be a halogen atom. 25. The method according to claims 22 to 24, characterized characterized in that one starts from substituting compounds through which a hydroxy, alkoxy, phenoxy, Naphthoxy, mercapto, amino or sulfone group in the dihydroxypyridine residue is introduced. 26. The method according to claims 22 to 25, characterized in that that azo compounds of the formula (6) are reacted with diamines in a molar ratio of 2: 1. 27 · 'The method according to claim 22 for the production of Heavy metal complexes of azo compounds, the remainder of the diazo component being a heterocyclic group and the remainder of the Coupling component contain the remainder of a 2,5-dihydroxypyridine, by reacting appropriate azo compounds with heavy metal releasing agents and optionally acylation. 28. The method according to claim 22, characterized in that that in metallization one or two molecules of azo compounds are used on one atom of metal. 209832/1146 29 · 'Method according to claim 2S ^ characterized in that that in the metallization one molecule of an azo compound of the formula (I) and one molecule that does not the remainder of a 2,3-dihydroxypyridine as a coupling component has to be used on an atom of metal. 30. The method according to claim 27, characterized in that that a cobalt, nickel or copper donor is used as the metal donor. 31 · The method according to claim 22 ^ characterized in that that you start from diazo or coupling components that contain a reactive radical, or that you have the finished azo compound or the heavy metal complex is acylated with an acylating agent which contains a reactive radical. 32. The method according to claim 31, characterized in that a diazo component is used which contains a reactive radical. 33 · The method according to claim 31, characterized in that that one uses diazo or coupling components which contain a water-solubilizing group. 209832/1 146 3 ^ · Method according to claims 22 to 33, characterized characterized in that one starts out from diazo components which contain a 5- or 6-membered heterocyclic radical. 35 · Process according to claims 22 to 3 ^ +, characterized in that that one starts from diazo components that contain a heterocyclic radical with 2 nitrogen atoms, 36. The method according to claims 22 to 35, characterized in that that one starts out from heterocyclic diazocorrons which contain a fused-on benzene residue. 37 · The method according to claims 22 to 36, characterized in characterized in that one azo dyes of the formula HO OH ( ⁶ ) D-NN- € ^ H where D is a quinoline radical bonded in the 8-position and Y is a halogen atom, verv, ^r ends as starting materials. 209832/11 U 6 3 & ·. Method according to claim 27, characterized in that that one is the diazo compound of the amine of the formula wherein Z is a halogen atom, a sulfonic acid, '. Acylamino or arylazo group is used as the diazo component. 59- Method according to claims 22 to 38, characterized characterized in that one uses high-polymer organic fibers, which contain reactive hydroxy, mercapto or amino groups as substituting compounds used." 40. The compounds obtained according to the examples. 41. Procedure according to the examples given. 42., · Use of the compounds according to the claims the/
1 to 21 or / according to claims 22 to 38 obtained Compounds as dyes or pigments. 43. "Method of dyeing and printing using the dyestuff according to claim 42. 44. The colored or printed according to claim 43 Material, especially the textile material. 2 09832/1146